US6960620B2 - Powder coating compositions comprising crystalline urethane acrylates and use thereof - Google Patents
Powder coating compositions comprising crystalline urethane acrylates and use thereof Download PDFInfo
- Publication number
- US6960620B2 US6960620B2 US10/325,933 US32593302A US6960620B2 US 6960620 B2 US6960620 B2 US 6960620B2 US 32593302 A US32593302 A US 32593302A US 6960620 B2 US6960620 B2 US 6960620B2
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- United States
- Prior art keywords
- acid
- group
- powder coating
- radiation
- diisocyanate
- Prior art date
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- Expired - Fee Related, expires
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2250/00—Compositions for preparing crystalline polymers
Definitions
- the present invention relates to radiation-curable powder coating compositions based on crystalline urethane acrylates, which crosslink to provide light-stable and weather-stable coating films.
- Thermal crosslinkable powder coating materials are known and are frequently used in the coatings-processing industry.
- DE-C 27 35 497 describes PU powder coatings having outstanding weathering stability and thermal stability.
- the crosslinkers whose preparation is described in DE-C 27 12 931 are composed of ⁇ -caprolactam-blocked isophorone diisocyanate containing isocyanurate groups.
- polyisocyanates containing urethane, biuret or urea groups whose isocyanate groups are likewise blocked.
- the disadvantage of these systems lies in the elimination of the blocking agent in the course of the thermal crosslinking reaction. Since the blocking agent may therefore be emitted into the environment, it is necessary on ecological and workplace safety grounds to take special precautions to clean the outgoing air and/or to recover the blocking agent. Moreover, the reactivity of the crosslinkers is low. Curing temperatures above 170° C. are required.
- EP 0636669 and WO 99/14254 describe two-component radiation-curable powder coating materials based on an unsaturated polyester and on a vinyl ether. The coatings produced from them are unsuitable for exterior use, since they yellow severely.
- thermoplastic resins containing from 0.5 to 3.5 polymerizable unsaturated groups per 1000 g molecular weight.
- the polyurethanes described are, however, not weather-stable and, on account of the absence of polyester groups and the low chain length, possess a low flexibility.
- EP 0934359 describes pulverulent, radiation-curable mixtures of amorphous and crystalline polyesters containing terminal methacrylate groups. The flexibility and adhesion of the powder coatings produced from these mixtures are no more than satisfactory.
- U.S. Pat. No. 5,639,560 describes radiation-curable powder compositions comprising special crystalline polyesters, containing methacrylate groups terminally, as binders.
- the binders are prepared by reacting crystalline polyesters with glycidyl methacrylate.
- the coatings produced from these powder coating compositions are very flexible.
- a radiation-curable powder coating composition comprising as binder at least one crystalline urethane acrylate having a melting point of 40-130° C.
- the invention provides radiation-curable powder coating compositions, comprising:
- compositions comprising:
- the invention further provides a process for preparing radiation-curable powder coating compositions, comprising:
- the invention also provides a process for producing coatings by using radiation-curable powder coating compositions comprising:
- the present invention provides a process for preparing a radiation-curable powder coating composition described above, comprising combining the binder (I) and the auxiliaries and additives (II).
- the present invention also provides a method of coating a substrate comprising applying the radiation-curable powder coating composition described above to the substrate.
- Urethane acrylates in the context of this invention are composed of a hydroxyl-containing polyester to which urethane groups and acrylate groups are attached by reaction with polyisocyanates and acrylate-functional alcohols.
- the crystalline urethane acrylates of the invention are prepared from crystalline, hydroxyl-containing polyesters (I.1) having a melting point of 40-130° C. by reaction with polyisocyanates (I.2) and a compound including both at least one alcohol group and at least one polymerizable acrylate group (I.3). They contain both urethane groups and terminal acrylate groups.
- This range for the melting point of the crystallization urethane acrylate includes all specific values and subranges therebetween, such as 50, 60, 70, 80, 90, 100, 110, 120, and 130° C.
- the crystalline, hydroxyl-containing polyesters I.1 having a melting point of 40-130° C. are prepared by polycondensation from appropriate dicarboxylic acids and diols. Condensation takes place conventionally in an inert gas atmosphere at temperatures from 100 to 260° C., preferably from 130 to 220° C., in the melt or in an azeotropic procedure, as described, for example, in Methoden der Organischen Chemie (Houben-Weyl); Volume 14/2, pages 1 to 5, 21 to 23, 40 to 44, Georg Thieme Verlag, Stuttgart, 1963, or in C. R. Martens, Alkyd Resins, pages 51 to 59, Reinhold Plastics Appl.
- carboxylic acids which are preferred for the preparation of polyesters may be aliphatic, cycloaliphatic and/or aromatic in nature. Examples thereof include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, endomethylenetetrahydrophthalic acid, glutaric acid, and—where obtainable—their anhydrides or esters.
- Suitable polyols include, for example, monoethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, di- ⁇ -hydroxyethylbutanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, decanediol, dodecanediol, neopentyl glycol, cyclohexanediol, 3(4),8(9)-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6 ]decane (Dicidol), 1,4-bis(hydroxymethyl)cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis[4-( ⁇ -hydroxyethoxy)phenyl]propane, 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 2,2,4(
- Crystalline, hydroxyl-containing polyesters prepared in this way have an OH number of 15-150 mg KOH/g, an acid number of ⁇ 5 mg KOH/g, and a melting point of 40-130° C. It is also possible to use mixtures of crystalline polyesters.
- Polyisocyanates I.2 used in the crystalline urethane acrylates of the invention include diisocyanates of aliphatic, (cyclo)aliphatic or cycloaliphatic structure.
- Representative examples of polyisocyanates are 2-methylpentamethylene 1,5-diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene 1,6-diisocyanate, especially the 2,2,4-isomer and the 2,4,4-isomer and technical-grade mixtures of both isomers, 4,4′-methylenebis(cyclohexyl isocyanate), norbornane diisocyanate, and 3,3,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (IPDI).
- polyisocyanates obtainable by reacting polyisocyanates with themselves by way of isocyanate groups, such as isocyanurates, which come about through reaction of three isocyanate groups.
- the polyisocyanates may likewise contain biuret or allophanate groups. IPDI is especially preferred.
- Suitable polymerizable compounds 1.3 having at least one free OH group and one polymerizable acrylate group include hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, and glycerol diacrylate. Hydroxyethyl acrylate (HEA) is especially preferred.
- OH-containing polyesters I.1, polyisocyanates I.2, and compounds I.3, first of all the polyisocyanate is introduced, DBTL catalyst and IONOL CP (Shell) polymerization inhibitor are added, and the polyester is added in an NCO:OH ratio of 2.5-1.5:1. Following these additions, the reaction is completed at 70-130° C. Thereafter, component I.3, e.g., hydroxyethyl acrylate in a residual NCO:OH ratio of 1.0-1.1:1 is added to the reaction product and the reaction is completed at 70-130° C., so that an NCO content of less than 0.1% is reached. Also possible is a preliminary reaction of a polyisocyanate, such as IPDI, with component I.3 and the addition of this NCO-functional precursor to the hydroxyl-containing crystalline polyester.
- a polyisocyanate such as IPDI
- Suitable means for radiation-curing the powder coating composition of the invention are accelerated electron beams.
- the electron beams generate free radicals from the powder coating composition, in a quantity sufficient to ensure extremely rapid polymerization of the reactive acrylate groups. It is preferred to use radiation doses of from 5 to 15 Mrad.
- UV initiators which are known in principle from conventional liquid UV-curing systems, e.g., EP 633912, incorporated herein by reference. These are substances which on irradiation with UV light break down into free radicals and so start the polymerization.
- suitable UV initiators include 2,2′-diethoxyacetophenone, hydroxycyclohexyl phenyl ketone, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, xanthone, thioxanthone, benzil dimethyl ketal, etc.
- UV initiators of this kind are offered commercially, e.g., IRGACURE 184 or DEGACURE 1173 from Ciba.
- the fraction of the photoinitiator in the overall system is from about 0.5 to 5% by weight.
- initiators such as thioxanthones, phosphine oxides, metallocenes, tertiary aminobenzenes or tertiary aminobenzophenones, which break down into free radicals on irradiation with visible light is likewise possible.
- Optional additives are acrylate- or methacrylate-functional compounds, such as the triacrylate of tris(2-hydroxyethyl) isocyanurate (SR 386, Sartomer), for example, and adhesion promoters, which can be used in minor amounts of 0-20% by weight in order to modify the coating properties.
- acrylate- or methacrylate-functional compounds such as the triacrylate of tris(2-hydroxyethyl) isocyanurate (SR 386, Sartomer), for example, and adhesion promoters, which can be used in minor amounts of 0-20% by weight in order to modify the coating properties.
- Further customary powder coatings additives include leveling agents, light stabilizers, and devolatilizers. These can be used at 0-5% by weight.
- pigments and extenders e.g., metal oxides such as titanium dioxide, and metal hydroxides, sulfates, sulfides, carbonates, silicates, talc, carbon black, etc., in weight fractions of 0-40%.
- the ingredients are mixed.
- the ingredients can be homogenized in suitable apparatus, such as heatable kneading apparatus, for example, but preferably by extrusion, in which case upper temperature limits of 120-130° C. ought not to be exceeded.
- suitable apparatus such as heatable kneading apparatus, for example, but preferably by extrusion, in which case upper temperature limits of 120-130° C. ought not to be exceeded.
- the extruded mass is ground to give the ready-to-spray powder, without the addition of refrigerants.
- Application of the ready-to-spray powder to appropriate substrates can be made by the known methods, such as by electrostatic or tribostatic powder spraying, fluidized-bed sintering or electrostatic fluid-bed sintering, for example.
- Suitable substrates are, for example, untreated or pretreated metallic substrates, wood, wood materials, plastics, glass or paper.
- the coatings produced from the powder coating compositions of the invention are weather-stable and highly flexible and possess good adhesion and excellent leveling. They can be formulated to range from highly glossy to matt.
- Acid components and alcohol components are admixed with 0.2 percent by mass of n-butyltin trioctanoate and the mixture is heated to 190° C. under nitrogen and with stirring in an apparatus provided with a distillation column. In the course of the water separation, this temperature is slowly raised to 230° C. After about 98% of the theoretical amount of water have been removed by distillation, the product is cooled and tested for OH number (OHN in mg KOH/g) and acid number (AN in mg KOH/g).
- polyesters were prepared in this way:
- BSA succinic anhydride
- DDS dodecanedioic acid
- DMT dimethyl terephthalate
- MEG monoethylene glycol
- BD 1,4-butanediol
- HD 1,6-hexanediol
- a mixture of 215.9 g of a 1:1 adduct of IPDI and hydroxyethyl acrylate, 2.0 g of IONOL CP and 0.1 g of DBTL is added in portions at 110° C. and with vigorous stirring to 772.0 g of the melted polyester A1 (OHN 35). After stirring for about an hour the NCO content is below 0.1% and the hot reaction mixture is poured from the flask onto a sheet. As soon as the reaction mass has solidified and cooled, it is mechanically comminuted and ground. The melting point of this product is 79° C.
- a mixture of 24.2 g of IPDI, 0.15 g of IONOL CP and 0.15 g of DBTL is added in portions at 120° C. and with vigorous stirring to 155.7 g of the melted polyester A3 (OHN 31). After reaction for 30 minutes a further 15.2 g of hydroxyethyl acrylate are added dropwise. After a further 45 minutes of stirring the NCO content is below 0.1% and the hot reaction mixture is poured from the flask onto a sheet. As soon as the reaction mass has solidified and cooled, it is mechanically comminuted and ground. The melting point of this product is 92° C.
- crystalline urethane acrylate A1U, A2U or A3U
- BYK 361 leveling agent, BYK Chemie
- Worlee Add 900 devolatilizer, Worlée-Chemie
- EBECRYL 170 adheresion promoter, UCB
- the extrudate is fractionated and ground using a pinned-disk mill, in the case of the comparative experiment with, and in the case of the inventive example without, the addition of refrigerants (liquid nitrogen or dry ice), to a particle size ⁇ 100 ⁇ m.
- the powder thus prepared is applied to degreased, optionally pretreated standard steel panels using an electrostatic powder spraying unit at 60 kV. The applied powder is then melted under IR irradiation and cured by means of electron beams (15 Mrad).
Abstract
Description
-
- I. a binder composed of at least one crystalline urethane acrylate with a melting point of from 40 to 130° C., and
- II. auxiliaries and additives.
-
- I. a binder composed of at least one crystalline urethane acrylate with a melting point of from 40 to 130° C., and
- II. auxiliaries and additives for preparing radiation-curable powder coating compositions.
-
- I. a binder composed of at least one crystalline urethane acrylate with a melting point of from 40 to 130° C., and
- II. auxiliaries and additives,
- observing an upper temperature limit of between 120° C. and 130° C., in heatable kneading apparatus, especially extruders.
-
- I. a binder composed of at least one crystalline urethane acrylate with a melting point of from 40 to 130° C., and
- II. auxiliaries and additives.
-
- A1: crystalline polyester from DDS 100%, MEG 100%, OHN 35 mg KOH/g, melting point 81° C.
- A2: crystalline polyester from BSA 100%, BD 100%, OHN 31 mg KOH/g, melting point 113° C.
- A3: crystalline polyester from DMT 60%, ADS 40%, HD 100%, OHN 31 mg KOH/g, melting point 96° C.
-
- 82.4 g Uracross P 3125 (DSM Resins)
- 16.9 g Uracross P 3307 (DSM Resins)
- 0.7 g Byk 361 (Byk-Chemie)
TABLE 1 | ||||||
Crystalline | ||||||
urethane | EC1 | Bl indir.2 | ||||
Experiment | acrylate | Substrate | [mm] | [inch-1b] | CC3 | ΔE4 |
1 | 100 A1U | Standard | >10 | >80 | 0 | 0.5 |
steel | ||||||
2 | 100 A2U | Standard | >10 | >80 | 0 | 0.8 |
steel | ||||||
3 | 100 A3U | Standard | >10 | >80 | 0 | 1.2 |
steel | ||||||
A | Comparison | Standard | 6.0 | <10 | 1 | 13.4 |
steel | ||||||
1Erichsen cupping (DIN 53 156, incorporated herein by reference) | ||||||
2Indirect ball impact (ASTM D 2797-93, incorporated herein by reference) | ||||||
3Cross-cut (DIN EN ISO 2409, incorporated herein by reference) (scale 0 (no loss of adhesion) to 5 (total loss of adhesion)) | ||||||
4Yellowing after 2000 h of QUV-A accelerated weathering (DIN 53384, incorporated herein by reference, and DIN ISO 4892-3, incorporated herein by reference) |
Claims (23)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10163825.6 | 2001-12-22 | ||
DE10163825A DE10163825A1 (en) | 2001-12-22 | 2001-12-22 | Powder coating compositions of crystalline urethane acrylates and their use |
Publications (2)
Publication Number | Publication Date |
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US20030175433A1 US20030175433A1 (en) | 2003-09-18 |
US6960620B2 true US6960620B2 (en) | 2005-11-01 |
Family
ID=7710771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/325,933 Expired - Fee Related US6960620B2 (en) | 2001-12-22 | 2002-12-23 | Powder coating compositions comprising crystalline urethane acrylates and use thereof |
Country Status (9)
Country | Link |
---|---|
US (1) | US6960620B2 (en) |
EP (1) | EP1323757B1 (en) |
JP (1) | JP2003192986A (en) |
AT (1) | ATE323116T1 (en) |
AU (1) | AU2002318860B2 (en) |
BR (1) | BR0205403A (en) |
CA (1) | CA2414947A1 (en) |
DE (2) | DE10163825A1 (en) |
ES (1) | ES2259689T3 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040138375A1 (en) * | 2002-12-24 | 2004-07-15 | Degussa Ag | Dispersons of amorphous urethanized unsaturated polyester resins based on particular dicidol isomers |
US20080152900A1 (en) * | 2006-12-22 | 2008-06-26 | Carmen Flosbach | Thermal curable powder coating composition |
US20080200577A1 (en) * | 2005-07-05 | 2008-08-21 | Emmanouil Spyrou | Method for Producing Radiation Curable Formulations with Increased Corrosion Protection on Metal Substrates, and Formulations of this Type |
US20100056662A1 (en) * | 2006-09-25 | 2010-03-04 | Evonik Degussa Gmbh | Radiation-curable formulation which forms flexible coatings with increased corrosion protection on metallic substrates |
US20100093884A1 (en) * | 2006-12-23 | 2010-04-15 | Evonik Degussa Gmbh | Radiation-curable formulations comprising silica and dispersant and featuring enhanced corrosion control on metal substrates |
US20110060068A1 (en) * | 2008-03-18 | 2011-03-10 | Evonik Degussa Gmbh | Radiation-curable formulations |
US8809412B2 (en) | 2007-08-25 | 2014-08-19 | Evonik Degussa Gmbh | Radiation-curable formulations |
US9122968B2 (en) | 2012-04-03 | 2015-09-01 | X-Card Holdings, Llc | Information carrying card comprising a cross-linked polymer composition, and method of making the same |
US9439334B2 (en) | 2012-04-03 | 2016-09-06 | X-Card Holdings, Llc | Information carrying card comprising crosslinked polymer composition, and method of making the same |
US9593135B2 (en) | 2012-10-23 | 2017-03-14 | Evonik Degussa Gmbh | Compositions comprising alkoxysilane-containing isocyanates and acid stabilisers |
US10029427B2 (en) | 2010-09-23 | 2018-07-24 | Evonik Degussa Gmbh | Process for the production of storage-stable polyurethane prepregs and mouldings produced therefrom from dissolved polyurethane composition |
US10093826B2 (en) | 2016-06-27 | 2018-10-09 | Evonik Degussa Gmbh | Alkoxysilane-functionalized allophanate-containing coating compositions |
US10633519B2 (en) | 2011-03-25 | 2020-04-28 | Evonik Operations Gmbh | Storage-stable polyurethane prepregs and mouldings produced therefrom composed of a polyurethane composition with liquid resin components |
US10906287B2 (en) | 2013-03-15 | 2021-02-02 | X-Card Holdings, Llc | Methods of making a core layer for an information carrying card, and resulting products |
US11361204B2 (en) | 2018-03-07 | 2022-06-14 | X-Card Holdings, Llc | Metal card |
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US20040209994A1 (en) * | 2002-12-19 | 2004-10-21 | Matthew Terwillegar | Polyester oligomers |
DE10346118A1 (en) | 2003-10-04 | 2005-09-22 | Degussa Ag | Powder coating compositions of urethane (meth) acrylates and micronized waxes and their use |
US20090155462A1 (en) * | 2007-12-18 | 2009-06-18 | Carmen Flosbach | Thermal curable polyester powder coating composition |
CN102245669A (en) | 2008-12-10 | 2011-11-16 | 纳幕尔杜邦公司 | Process for the preparation of polyuretdione resins |
WO2016080439A1 (en) * | 2014-11-18 | 2016-05-26 | 日本合成化学工業株式会社 | Active-energy-ray-curable composition, active-energy-ray-curable adhesive composition, adhesive, adhesive sheet, and novel urethane (meth)acrylate |
JP6874504B2 (en) * | 2016-04-26 | 2021-05-19 | 大日本印刷株式会社 | Multi-layer laminated film for laser printing and packaging and printing materials made of it |
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2001
- 2001-12-22 DE DE10163825A patent/DE10163825A1/en not_active Withdrawn
-
2002
- 2002-11-06 ES ES02024720T patent/ES2259689T3/en not_active Expired - Lifetime
- 2002-11-06 AT AT02024720T patent/ATE323116T1/en not_active IP Right Cessation
- 2002-11-06 EP EP02024720A patent/EP1323757B1/en not_active Expired - Lifetime
- 2002-11-06 DE DE50206376T patent/DE50206376D1/en not_active Expired - Lifetime
- 2002-12-17 BR BR0205403-5A patent/BR0205403A/en not_active Application Discontinuation
- 2002-12-18 AU AU2002318860A patent/AU2002318860B2/en not_active Expired - Fee Related
- 2002-12-20 CA CA002414947A patent/CA2414947A1/en not_active Abandoned
- 2002-12-23 US US10/325,933 patent/US6960620B2/en not_active Expired - Fee Related
- 2002-12-24 JP JP2002373116A patent/JP2003192986A/en active Pending
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Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
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US20040138375A1 (en) * | 2002-12-24 | 2004-07-15 | Degussa Ag | Dispersons of amorphous urethanized unsaturated polyester resins based on particular dicidol isomers |
US7135522B2 (en) * | 2002-12-24 | 2006-11-14 | Degussa Ag | Dispersions of amorphous urethanized unsaturated polyester resins based on particular dicidol isomers |
US8222312B2 (en) | 2005-07-05 | 2012-07-17 | Evonik Degussa Gmbh | Method for producing radiation curable formulations with increased corrosion protection on metal substrates, and formulations of this type |
US20080200577A1 (en) * | 2005-07-05 | 2008-08-21 | Emmanouil Spyrou | Method for Producing Radiation Curable Formulations with Increased Corrosion Protection on Metal Substrates, and Formulations of this Type |
US20100056662A1 (en) * | 2006-09-25 | 2010-03-04 | Evonik Degussa Gmbh | Radiation-curable formulation which forms flexible coatings with increased corrosion protection on metallic substrates |
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EP1323757B1 (en) | 2006-04-12 |
ES2259689T3 (en) | 2006-10-16 |
EP1323757A3 (en) | 2004-01-02 |
CA2414947A1 (en) | 2003-06-22 |
DE10163825A1 (en) | 2003-07-03 |
DE50206376D1 (en) | 2006-05-24 |
US20030175433A1 (en) | 2003-09-18 |
EP1323757A2 (en) | 2003-07-02 |
AU2002318860B2 (en) | 2006-11-02 |
JP2003192986A (en) | 2003-07-09 |
ATE323116T1 (en) | 2006-04-15 |
BR0205403A (en) | 2004-07-20 |
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